Chemically amplified negative resist composition and resist pattern forming process

Abstract

A chemically amplified negative resist composition comprising (A) a photoacid generator in the form of an onium salt containing an aromatic sulfonic acid anion having a bulky substituent-bearing aromatic ring structure and a fluorinated substituent and (B) a base polymer is provided. The resist composition exhibits a high resolution during pattern formation and forms a pattern with reduced LER and fidelity.

1 . A chemically amplified negative resist composition comprising (A) a photoacid generator in the form of an onium salt having the formula (A) and (B) a base polymer containing a polymer comprising repeat units having the formula (B1), 
       
         
           
           
               
               
           
         
       
       wherein n1 and n2 are each independently an integer of 0 to 2, n3 is an integer of 1 to 4 in case of n2=0, an integer of 1 to 6 in case of n2=1, and an integer of 1 to 8 in case of n2=2, n4 is an integer of 0 to 3 in case of n2=0, an integer of 0 to 5 in case of n2=1, and an integer of 0 to 7 in case of n2=2, n3+n4 is an integer of 1 to 4 in case of n2=0, an integer of 1 to 6 in case of n2=1, and an integer of 1 to 8 in case of n2=2, n5 is an integer of 1 to 5 in case of n1=0, an integer of 1 to 7 in case of n1=1, and an integer of 1 to 9 in case of n1=2,
 R 1  is iodine or a C 3 -C 20  branched or cyclic hydrocarbyl group which may contain a heteroatom, at least one R 1  is bonded to a carbon atom adjoining the carbon atom to which L A  is bonded, a plurality of R 1  may bond together to form a ring with the carbon atoms to which they are attached when n5 is 2 or more, 
 R 2  is a C 1 -C 20  hydrocarbyl group which may contain a heteroatom, a plurality of R 2  may bond together to form a ring with the carbon atoms to which they are attached when n4 is 2 or more, 
 R F1  is fluorine, a C 1 -C 6  fluorinated alkyl group, C 1 -C 6  fluorinated alkoxy group, or C 1 -C 6  fluorinated thioalkoxy group, 
 L A  and L B  are each independently a single bond, ether bond, ester bond, amide bond, sulfonate ester bond, carbonate bond or carbamate bond, and 
 X L  is a single bond or a C 1 -C 40  hydrocarbylene group which may contain a heteroatom, and 
 Z +  is an onium cation, 
 
       
         
           
           
               
               
           
         
       
       wherein a1 is 0 or 1, a2 is 0, 1 or 2, a3 is an integer satisfying 0≤a3≤5+2 (a2)−a4, a4 is 1, 2 or 3,
 R A  is hydrogen, fluorine, methyl or trifluoromethyl, 
 R 11  is halogen, an optionally halogenated C 1 -C 6  saturated hydrocarbyl group, optionally halogenated C 1 -C 6  saturated hydrocarbyloxy group, or optionally halogenated C 2 -C 8  saturated hydrocarbylcarbonyloxy group, and 
 A 1  is a single bond or a C 1 -C 10  saturated hydrocarbylene group in which some —CH 2 — may be replaced by —O—. 
 
     
     
         2 . The negative resist composition of  claim 1  wherein Z +  is a sulfonium cation having the formula (cation-1) or iodonium cation having the formula (cation-2): 
       
         
           
           
               
               
           
         
       
       wherein R ct1  to R ct5  are each independently halogen or a C 1 -C 30  hydrocarbyl group which may contain a heteroatom, and R ct1  and R ct2  may bond together to form a ring with the sulfur atom to which they are attached. 
     
     
         3 . The negative resist composition of  claim 1  wherein the polymer further comprises repeat units of at least one type selected from repeat units having the formula (B2) and repeat units having the formula (B3): 
       
         
           
           
               
               
           
         
       
       wherein b1 is 0 or 1, b2 is 0, 1 or 2, b3 is an integer satisfying 0≤b3≤5+2 (b2)−b4, b4 is 1, 2 or 3, b5 is 0, 1 or 2, b6 is 1 or 2,
 R A  is each independently hydrogen, fluorine, methyl or trifluoromethyl, 
 R 12  is halogen or a C 1 -C 20  hydrocarbyl group which may contain a heteroatom, 
 R 13  and R 14  are each independently hydrogen, a C 1 -C 15  saturated hydrocarbyl group or C 6 -C 15  aryl group, the hydrocarbyl group may be substituted with hydroxy or a C 1 -C 6  saturated hydrocarbyloxy moiety, the aryl group may have a substituent, excluding that R 13  and R 14  are hydrogen at the same time, R 13  and R 14  may bond together to form a ring with the carbon atom to which they are attached, some —CH 2 — in the ring may be replaced by —O— or —S—, 
 R 15  is halogen or a C 1 -C 20  hydrocarbyl group which may contain a heteroatom, 
 R 16  and R 17  are each independently hydrogen, a C 1 -C 15  saturated hydrocarbyl group or C 6 -C 15  aryl group, the hydrocarbyl group may be substituted with hydroxy or a C 1 -C 6  saturated hydrocarbyloxy moiety, the aryl group may have a substituent, excluding that R 16  and R 17  are hydrogen at the same time, R 16  and R 17  may bond together to form a ring with the carbon atom to which they are attached, some —CH 2 — in the ring may be replaced by —O— or —S—, 
 A 2  is a single bond or a C 1 -C 10  saturated hydrocarbylene group in which some —CH 2 — may be replaced by —O—, 
 W 1  and W 2  are each independently hydrogen, a C 1 -C 10  aliphatic hydrocarbyl group, C 2 -C 10  aliphatic hydrocarbylcarbonyl group or C 6 -C 15  aryl group, the aryl group may have a substituent. 
 
     
     
         4 . The negative resist composition of  claim 1  wherein the polymer further comprises repeat units of at least one type selected from repeat units having the formula (B4), repeat units having the formula (B5), and repeat units having the formula (B6): 
       
         
           
           
               
               
           
         
       
       wherein c and d are each independently an integer of 0 to 4, e1 is 0 or 1, e2 is 0, 1 or 2, e3 is an integer of 0 to 5,
 R A  is hydrogen, fluorine, methyl or trifluoromethyl, 
 R 21  and R 22  are each independently hydroxy, halogen, an optionally halogenated C 1 -C 8  saturated hydrocarbyl group, optionally halogenated C 1 -C 8  saturated hydrocarbyloxy group, or optionally halogenated C 2 -C 8  saturated hydrocarbylcarbonyloxy group, 
 R 23  is a C 1 -C 20  saturated hydrocarbyl group, C 1 -C 20  saturated hydrocarbyloxy group, C 2 -C 20  saturated hydrocarbylcarbonyloxy group, C 2 -C 20  saturated hydrocarbyloxyhydrocarbyl group, C 2 -C 20  saturated hydrocarbylthiohydrocarbyl group, halogen, nitro group, cyano group, C 1 -C 20  saturated hydrocarbylsulfinyl group, or C 1 -C 20  saturated hydrocarbylsulfonyl group, 
 A 3  is a single bond or C 1 -C 10  saturated hydrocarbylene group in which some —CH 2 — may be replaced by —O—. 
 
     
     
         5 . The negative resist composition of  claim 3  wherein the polymer further comprises repeat units of at least one type selected from repeat units having the formulae (B7) to (B14): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein R B  is each independently hydrogen or methyl,
 Y 1  is each independently a single bond, a C 1 -C 6  aliphatic hydrocarbylene group, phenylene group, naphthylene group or C 7 -C 18  group obtained by combining the foregoing, *—O—Y 11 —, *—C(═O)—O—Y 11 —, or *—C(═O)—NH—Y 11 —, Y 11  is a C 1 -C 6  aliphatic hydrocarbylene group, phenylene group, naphthylene group or C 7 -C 18  group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety, 
 Y 2  is each independently a single bond or **—Y 21 —C(═O)—O—, Y 21  is a C 1 -C 20  hydrocarbylene group which may contain a heteroatom, 
 Y 3  is each independently a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, *—O—Y 31 —, *—C(═O)—O—Y 31 —, or *—C(═O)—NH—Y 31 —, Y 31  is a C 1 -C 6  aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, trifluoromethyl-substituted phenylene group, or C 7 -C 20  group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety, 
 * designates a point of attachment to the carbon atom in the backbone, ** designates a point of attachment to the oxygen atom in the formula, 
 Y 4  is each independently a single bond or C 1 -C 30  hydrocarbylene group which may contain a heteroatom, 
 f1 and f2 are each independently 0 or 1, f1 and f2 are 0 when Y 4  is a single bond, 
 R 31  to R 48  are each independently halogen or a C 1 -C 20  hydrocarbyl group which may contain a heteroatom, R 31  and R 32  may bond together to form a ring with the sulfur atom to which they are attached, R 33  and R 34 , R 36  and R 37 , or R 39  and R 40  may bond together to form a ring with the sulfur atom to which they are attached, 
 R HF  is hydrogen or trifluoromethyl, and 
 Xa −  is a non-nucleophilic counter ion. 
 
     
     
         6 . The negative resist composition of  claim 5  wherein the polymer comprises repeat units having the formula (B1-1), repeat units having the formula (B2-1), (B2-2) or (B3-1), and repeat units having the formula (B8): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein a4, b4, b6, R A , R B , Y 2 , R 13 , R 14 , R 16 , R 17 , R 33 , R 34 , R 35 , and R HF  are as defined above. 
     
     
         7 . The negative resist composition of  claim 5  wherein the base polymer (B) further contains a polymer comprising repeat units having formula (B1) and repeat units having formula (B2) or (B3), but not repeat units having formulae (B7) to (B14). 
     
     
         8 . The negative resist composition of  claim 1  wherein repeat units having an aromatic ring structure account for at least 60 mol % of the overall repeat units of the polymer in the base polymer. 
     
     
         9 . The negative resist composition of  claim 1 , further comprising (C) a crosslinker. 
     
     
         10 . The negative resist composition of  claim 3  which is free of a crosslinker. 
     
     
         11 . The negative resist composition of  claim 1 , further comprising (D) a fluorinated polymer comprising repeat units of at least one type selected from repeat units having the formula (D1), repeat units having the formula (D2), repeat units having the formula (D3) and repeat units having the formula (D4) and optionally repeat units of at least one type selected from repeat units having the formula (D5) and repeat units having the formula (D6): 
       
         
           
           
               
               
           
         
       
       wherein x is an integer of 1 to 3, y is an integer satisfying 0≤y≤5+2z−x, z is 0 or 1, g is an integer of 1 to 3,
 R C  is each independently hydrogen, fluorine, methyl or trifluoromethyl, 
 R D  is each independently hydrogen or methyl, 
 R 101 , R 102 , R 104  and R 105  are each independently hydrogen or a C 1 -C 10  saturated hydrocarbyl group, 
 R 103 , R 106 , R 107  and R 108  are each independently hydrogen, a C 1 -C 15  hydrocarbyl group, C 1 -C 15  fluorinated hydrocarbyl group, or acid labile group, and when R 103 , R 106 , R 107  and R 108  each are a hydrocarbyl or fluorinated hydrocarbyl group, an ether bond or carbonyl moiety may intervene in a carbon-carbon bond, 
 R 109  is hydrogen or a C 1 -C 5  straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond, 
 R 110  is a C 1 -C 5  straight or branched hydrocarbyl group in which a heteroatom-containing moiety may intervene in a carbon-carbon bond, 
 R 111  is a C 1 -C 20  saturated hydrocarbyl group in which at least one hydrogen is substituted by fluorine, and in which some —CH 2 — may be replaced by an ester bond or ether bond, 
 Z 1  is a C 1 -C 20  (g+1)-valent hydrocarbon group or C 1 -C 20  (g+1)-valent fluorinated hydrocarbon group, 
 Z 2  is a single bond, *—C(═O)—O— or *—C(═O)—NH—, * designates a point of attachment to the carbon atom in the backbone, 
 Z 3  is a single bond, —O—, *—C(═O)—O—Z 31 —Z 32 — or *—C(═O)—NH—Z 31 —Z 32 , Z 31  is a single bond or C 1 -C 10  saturated hydrocarbylene group, Z 32  is a single bond, ester bond, ether bond, or sulfonamide bond, and * designates a point of attachment to the carbon atom in the backbone. 
 
     
     
         12 . The negative resist composition of  claim 1 , further comprising (E) a quencher. 
     
     
         13 . The negative resist composition of  claim 1 , further comprising (F) an organic solvent. 
     
     
         14 . A resist pattern forming process comprising the steps of:
 applying the chemically amplified negative resist composition of  claim 1  onto a substrate to form a resist film thereon,   exposing the resist film patternwise to high-energy radiation, and   developing the exposed resist film in an alkaline developer.   
     
     
         15 . The process of  claim 14  wherein the high-energy radiation is EUV or EB. 
     
     
         16 . The process of  claim 14  wherein the substrate has the outermost surface of a material containing at least one element selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin. 
     
     
         17 . The process of  claim 14  wherein the substrate is a mask blank of transmission or reflection type. 
     
     
         18 . A mask blank of transmission or reflection type which is coated with the chemically amplified negative resist composition of  claim 1 .